Synthetic Pathways for New Tubular Transition Metal Hydroxo- and Fluoro-Selenites: Crystal Structures ofM12(X)2(SeO3)8(OH)6(M=Co2+,Ni2+;X= OH−)

Amorós, Pedro; Marcos, M. Dolores; Roca, Manuel; Beltrán-Porter, Daniel

doi:10.1006/jssc.1996.0325

Cited by 18 publications

(16 citation statements)

References 14 publications

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“…The transition metal chalcogenites have the general stoichiometry (M 2 OH) 3 (TO 3 ) 4 X with T = Se 4+ or Te 4+ , M = Ni 2+ or Co 2+ , and X = OHor F - (Perez et al 1976, Amorós et al 1996. They are unique among the DLMs in having the X sites in the hexagonal channel occupied by anions.…”

Section: Tm Chalcogenitesmentioning

confidence: 99%

“…As in ekatite and the hypothetical Si-free dumortierite-holtite endmembers, this leads to a lack of coordinating anions around the hexagonal channel, and thus no cations at the X site. However, the [(M 2 OH) 3 (TO 3 ) 4 + ] framework is positively charged, and so small monovalent "guest" anions OHor Fare incorporated into the hexagonal channel for charge balance (Marcos et al 1993a, Amorós et al 1996. The X anions are octahedrally coordinated by the lone pairs of electrons on the chalcogens.…”

Section: Tm Chalcogenitesmentioning

confidence: 99%

“…Several classes of synthetic compounds isostructural with hexagonal ellenbergerite have been produced via hydrothermal synthesis: the first-row divalent transition metal (TM) phosphites (Marcos et al 1993b, 1993c, Attfield et al 1994, Che et al 2005, Gu et al 2007, Ni et al 2009, Jin et al 2010, Liao & Ni 2010, metal pnictates (phosphates and arsenates) (Marcos et al 1993a, Hughes et al 2003, the TM chalcogenites (selenites and tellurites) (Perez et al 1976, Amorós et al 1996, and the metal vanadates and sulfate-vanadates (Kato et al 1998, Zhang et al 1999, Ðođević et al 2008, Hu et al 2008. Each of these compounds show crystal-chemical features seen in the dumortierite-and ellenbergerite-group minerals, as well as some novel features.…”

Section: Introductionmentioning

confidence: 99%

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Structure and Topology of Dumortierite and Dumortierite-Like Materials

Evans

Groat

2012

The Canadian Mineralogist

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Dumortierite, ca. (Al,)Al 6 (BO 3)Si 3 O 13 (O,OH) 2 , has a complex and unusual crystal structure that is shared by several minerals and an increasing number of synthetic materials, which we group together as dumortierite-like materials (DLMs). Dumortierite has a strongly pseudo-hexagonal orthorhombic structure based on rod-like double-chains of Al octahedra in a framework based on the {6•4•3•4} semi-regular planar tiling. The large hexagonal channels contain chains of face-sharing Al octahedra attached to the framework by rings of SiO 4 tetrahedra. Smaller triangular channels contain planar BO 3 groups, while in other materials the triangular channels are occupied by tetrahedral or pyramidal groups. Holtite and magnesiodumortierite are isostructural with dumortierite, while ellenbergerite, phosphoellenbergerite, ekatite, and the synthetic materials have very similar structures to dumortierite, but with hexagonal symmetry. These minerals and materials differ from one another in the identity of the metal cations occupying the framework and face-sharing chains, and in the tetrahedral, pyramidal, or triangular groups within the hexagonal and triangular channels. We write the following structure-generating function, which describes both topological and stoichiometric properties of DLMs: X(M 2 Φ) 3 (T h Q h 3 q h) 3 (T t Q t 3 q t) where X is the face-sharing hexagonal channel octahedrally coordinated site, M is the framework octahedrally coordinated site, T h and T t are three-to four-coordinate cation sites in the hexagonal and triangular channels, Φ is a four-coordinate anion site, Q h and Q t are three-coordinate basal anion sites, and q h and q t are one-to three-coordinate apical anion sites. We discuss various structural and crystal chemical properties of DLMs, illustrating their commonalities as variations on the theme described by the structure-generating function. We also discuss three closely related structures which involve modifications of different geometrical or topological aspects of the DLM structure: the structure of lyonsite and its synthetic analogues, the structure of satterlyite and holtedahlite, and the structure of the AB polytype of the cancrinite group of feldspathoids.

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Section: Tm Chalcogenitesmentioning

confidence: 99%

Section: Tm Chalcogenitesmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Structure and Topology of Dumortierite and Dumortierite-Like Materials

Evans

Groat

2012

The Canadian Mineralogist

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“…The presence of OH at the 4-coordinated O10 site is supported by bond valence analysis of the dumortierite structure, which shows O10 is underbonded, consistent with partial replacement of O by OH ; OH is known to occupy the O10 position in magnesiodumortierite, which has a higher water content than dumortierite. The minerals ellenbergerite and phosphoellenbergerite, whose structures are hexagonal analogues of the dumortierite structure, are believed to contain OH at the 4-coordinated oxygen site equivalent to O10 in dumortierite (Raade et al 1998;Brunet and Schaller 1996), as do several classes of synthetic materials with similar crystal structures (e.g., Marcos et al 1993;Amorós et al 1996), as well as the mineral holtedahlite, which has a different overall structure but features double octahedral chains similar to those that host the Al4 and O10 sites in dumortierite (Brunet and Schaller 1996). There is less evidence for OH at the O9 or O1 positions (Fuchs et al 2005).…”

Section: Crystallography Of Dumortierite and Holtitementioning

confidence: 99%

MAS NMR measurements and ab initio calculations of the 29Si chemical shifts in dumortierite and holtite

Evans

Fyfe

Groat

et al. 2012

American Mineralogist

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Three samples from the dumortierite group of minerals were examined with magic angle spinning nuclear magnetic resonance spectroscopy (MAS NMR): a dumortierite [c. (Al,)Al 6 (BO 3 ) Si 3 O 13 (O,OH) 2 ] consisting of dark blue euhedral crystals from Madagascar (D34); a fine-grained pale blue dumortierite from Island Copper mine, British Columbia, Canada (D12); and a creamy white holtite [c. (Ta,Nb,,Al)Al 6 (BO 3 )(Si,Sb,As) 3 O 12 (O,OH,) 3 ] from Szklary, Lower Silesia, Poland (WPH). Restricted Hartree-Fock ab initio electronic structure calculations were performed on model clusters with the goal of matching local environments of Si atoms to peaks in the 29 Si MAS NMR spectra. The spectrum of D34 showed five resolved peaks at -95.2, -92.6, -91.3, -89.1, and -86.5 ppm with deconvoluted peak area contributions of 57, 19, 7, 10, and 7%. Electronic structure calculations, cross-polarization MAS NMR measurements and relative intensities support assigning the peaks at -95.2 and -92.6 ppm to Si2 and Si1 sites, respectively, adjacent to fully occupied Al1 sites (i.e., Q 4 Si sites), and assigning the three remaining peaks to Si sites adjacent to vacant Al1 sites (i.e., Q 3 Si sites). Due to the complexity of the dumortierite structure, clusters composed of at least the first four shells of nearest neighbor atoms to the target Si atom are necessary to model Q 4 sites. The spectrum of D12 showed two main peaks at -93 and -95 ppm, with minor peaks below -90 ppm and above -100 ppm. The spectrum of WPH showed one broad peak at -93 ppm, likely containing both Si1 and Si2 signals, and two minor peaks below -90 ppm.Single-crystal X-ray diffraction and structure refinement on D34 shows orthorhombic symmetry, Pnma, Z = 4, a = 4.6882(1), b = 11.7924(2), c = 20.1856(3) Å, and V = 1115.97(4) Å 3 with R 1 = 0.0124. Three distinct sub-sites of the face-sharing octahedral chain site Al1 were distinguished corresponding to sites with one vacancy above, with one vacancy below, and between two occupied sites; the vacancy-adjacent sites have the cation displaced to increase the Al 3+ -Al 3+ distance. Each sub-site is approximately ¼ occupied, suggesting that Al 3+ cations in individual face-sharing octahedral chains are ordered as -Al-Al-Al, although cations from chain to chain are disordered, preserving Pnma symmetry.Powder X-ray diffraction measurements were performed on both D34 and D12. The unit cell of D12 was found to be a = 4.7001(7), b = 11.785(2), c = 20.277(3) Å.

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“…It is based on co-precipitaion of metallic selenites precursors in aqueous medium [38][39][40][41][42][43] . After deposition by Doctor Blade technique, the layer is thermal treated in sulfur atmosphere.…”

Section: Introductionmentioning

confidence: 99%

Easy and low-cost aqueous precipitation method to obtain Cu2ZnSn(S, Se)4 thin layers

Martí

Lyubenova

Roures

et al. 2017

Solar Energy Materials and Solar Cells

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Abstract:An easy method to obtain kesterite Cu2ZnSn(Se1-x,Sx)4 (CZTSSe) solid solution as an absorber for thin film photovoltaic solar cells is discussed in this report. Particular emphasis is directed toward the procedure´s steps of the CZTSSe preparation, as well as its structure and properties. For the preparation of CZTSSe an easy, low-cost and sustainable aqueous precipitation method that included chemical transformations of metal selenite precipitate, its reduction to metal selenides and further crystallization of kesterite, is applied. This procedure is more viable as avoids the use of selenization treatment and thus generation of toxic vapors and employs water as a solvent instead of organic compounds. In addition, the proposed procedure is very attractive way of preparation for industrial large-scale fabrication of the most promising absorber candidates for photovoltaic thin film solar cells.Kesterite CZTSSe solid solution has been prepared and characterized in terms of chemical composition, structural and morphological transformations, as well as optical and electrical properties, confirming the viability and effectiveness of the applied process.The optimal electrical parameters obtained of the device are 21.5 mA/cm2, 532 mV, 42.8%., and 4.9% to short circuit current (Jsc), open circuit voltage (Voc), fill factor (FF), and efficiency (Eff.) respectively. Detailed description of each procedure steps and full characterization of the products, starting from as-prepared, intermediate and final compound is also exposed that could be very useful for any experimental scientist.2

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Synthetic Pathways for New Tubular Transition Metal Hydroxo- and Fluoro-Selenites: Crystal Structures ofM12(X)2(SeO3)8(OH)6(M=Co2+,Ni2+;X= OH−)

Cited by 18 publications

References 14 publications

Structure and Topology of Dumortierite and Dumortierite-Like Materials

Structure and Topology of Dumortierite and Dumortierite-Like Materials

MAS NMR measurements and ab initio calculations of the 29Si chemical shifts in dumortierite and holtite

Easy and low-cost aqueous precipitation method to obtain Cu2ZnSn(S, Se)4 thin layers

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